Abstract Molecular ions formed in cold hybrid ion-atom experiments may find interesting applications ranging from precision measurements to controlled chemical reactions. Here, we investigate electronic structure of the Sr2 + molecular ion, which may be produced by photoassociation of laser-cooled Sr+ ions immersed into an ultracold gas of Sr atoms or by ionization of ultracold Sr2 molecules. Using ab initio electronic structure methods, such as the coupled cluster and configuration interaction ones with small-core relativistic energy-consistent pseudopotentials and large Gaussian basis sets, we calculate potential energy curves for the ground and 41 excited electronic states, and electric dipole transition moments between them. We show that alkaline-earth molecular ions despite of their apparently simple structure with three valence electrons only are challenging for state-of-the-art quantum chemistry methods due to their multireference nature and high density of states. Finally, we calculate and analyze Franck-Condon factors governing the photoionization of ground-state Sr2 molecules into 2Σu + and 2Σg + states of Sr2 + molecular ions. The present results may be useful for studying and guiding formation and spectroscopy of cold Sr2 + molecular ions.
Abstract Molecular ions formed in cold hybrid ion-atom experiments may find interesting applications ranging from precision measurements to controlled chemical reactions. Here, we investigate electronic structure of the Sr2 + molecular ion, which may be produced by photoassociation of laser-cooled Sr+ ions immersed into an ultracold gas of Sr atoms or by ionization of ultracold Sr2 molecules. Using ab initio electronic structure methods, such as the coupled cluster and configuration interaction ones with small-core relativistic energy-consistent pseudopotentials and large Gaussian basis sets, we calculate potential energy curves for the ground and 41 excited electronic states, and electric dipole transition moments between them. We show that alkaline-earth molecular ions despite of their apparently simple structure with three valence electrons only are challenging for state-of-the-art quantum chemistry methods due to their multireference nature and high density of states. Finally, we calculate and analyze Franck-Condon factors governing the photoionization of ground-state Sr2 molecules into 2Σu + and 2Σg + states of Sr2 + molecular ions. The present results may be useful for studying and guiding formation and spectroscopy of cold Sr2 + molecular ions.
Abstract Molecular ions formed in cold hybrid ion–atom experiments may find interesting applications ranging from precision measurements to controlled chemical reactions. Here, we investigate the electronic structure of the Sr 2 + molecular ion, which may be produced by photoassociation of laser-cooled Sr+ ions immersed in an ultracold gas of Sr atoms or by ionization of ultracold Sr2 molecules. Using ab initio electronic structure methods, such as the coupled cluster and configuration interaction ones with small-core relativistic energy-consistent pseudopotentials and large Gaussian basis sets, we calculate potential energy curves for the ground and 41 excited electronic states, and electric dipole transition moments between them. We show that alkaline-earth molecular ions, despite their apparently simple structure with only three valence electrons, are challenging for state-of-the-art quantum chemistry methods due to their multireference nature and high density of states. Finally, we calculate and analyze Franck–Condon factors governing the photoionization of ground-state Sr2 molecules into Σ u + 2 and Σ g + 2 states of Sr 2 + molecular ions. The present results may be useful for studying and guiding the formation and spectroscopy of cold Sr 2 + molecular ions.
In this work, a comprehensive theoretical investigation is carried out to explore the electronic and spectroscopic properties of selected diatomic molecular ions MgRb+ and SrRb+. Using high-level ab initio calculations based on a pseudopotential approach, along with large Gaussian basis sets and full valence configuration interaction (FCI), we accurately determine adiabatic potential energy curves, spectroscopic constants, transition dipole moments (TDMs), and permanent electric dipole moments (PDMs). To deepen our understanding of these systems, we calculate radiative lifetimes for vibrational levels in both ground and low-lying excited electronic states. This includes evaluating spontaneous and stimulated emission rates, as well as the effects of blackbody radiation. We also compute Franck–Condon factors and analyze photoassociation processes for both ions. Furthermore, to explore low-energy collisional dynamics, we investigate elastic scattering in the first excited states (21Σ+) describing the collision between the Ra atom and Mg+ or Sr+ ions. Our findings provide detailed insights into the theoretical electronic structure of these molecular ions, paving the way for future experimental studies in the field of cold and ultracold molecular ion physics.
Abstract Experiments with cold ion–atom mixtures have recently opened the way for the production and application of ultracold molecular ions. Here, in a comparative study, we theoretically investigate ground and several excited electronic states and prospects for the formation of molecular ions composed of a calcium ion and an alkali-metal atom: CaAlk+ (Alk = Li, Na, K, Rb, Cs). We use a quantum chemistry approach based on non-empirical pseudopotentials, operatorial core-valence correlation, large Gaussian basis sets, and full configuration interaction method for valence electrons. Adiabatic potential energy curves, spectroscopic constants, and transition and permanent electric dipole moments are determined and analyzed for the ground and excited electronic states. We examine the prospects for ion-neutral reactive processes and the production of molecular ions via spontaneous radiative association and laser-induced photoassociation. After that, spontaneous and stimulated blackbody radiation transition rates are calculated and used to obtain radiative lifetimes of vibrational states of the ground and first-excited electronic states. The present results pave the way for the formation and spectroscopy of calcium–alkali-metal-atom molecular ions in modern experiments with cold ion–atom mixtures.
Abstract Alkaline-earth and alkali-metal mixtures have an electronic structure that is perfect for laser cooling. This makes them highly attractive for trapping and laser cooling experiments, allowing the formation of cold molecules. For this object, potential-energy curves and relevant spectroscopic parameters of the low-lying electronic excited states of 1,3Σ+, 1,3Π, and 1,3Δ symmetries of molecular-ion systems composed of alkaline-earth-ion and Francium alkali-metal-atom: ALKE-Fr+ (ALKE = Be, Mg, Ca and Sr), are determined using advanced theoretical technique in quantum chemistry, including a non-empirical pseudopotential, core-valence correlation, large Gaussian basis sets and Full Configuration Interaction (FCI). In order to obtain a more accurate understanding of the electronic structure of these systems, we also determined transition and permanent dipole moments and vibrational properties. Thereafter, the spontaneous and the black-body stimulated transition rates were determined and were employed to calculate lifetimes for all vibrational states of the ground electronic states 11Σ+ of molecular-ions under consideration. For the first and the second excited states, radiative lifetimes were investigated via the Franck–Condon approximation including bound-bound and bound-free transitions. High diagonal structure and large Franck Condon Factor (FCF) values f 00 = 0.987, f 11 = 0.959 and f 22 = 0.919 were obtained for the 11Π (v′ = 0, 1, 2)→ 11Σ+ (v = 0, 1, 2) transition making the BeFr+ system a good candidate for laser cooling. Furthermore, the current results could be used to investigate elastic scattering properties in cold-ion-atom collisions for the first excited states and may help the experimentalists for possible formation, spectroscopy, and photoassociation of cold ion-atom mixtures.
The adiabatic potential energy curves, permanent and transition dipole moments (TDMs) of the highly-excited states of the MgK + molecular ion have been computed as a function of the inter-nuclear distance R. The results are obtained by an ab initio approach involving a non-empirical pseudo-potential for the Mg and K cores, correlation treatment for core valence through an effective core polarisation potential, and full valence configuration interaction. The molecule is thus treated as a two electron system. Ab initio electronic TDM functions are calculated for all dipole-allowed transitions among the 42 states of MgK + . Many of these moment functions exhibit interesting behaviour due to charge transfer or ion-atom pair correlations. The positions of a number of satellite bands are predicted from the potential energy difference curves. We verified our results by performing complete active space self-consistent field calculations followed by a multireference configuration interaction and including Davidson correction. We observe a rather good agreement for most of them especially for the ground and lower excited states. We investigate ion-atom cold collisions at quantum regime. Furthermore, we explore ion-atom elastic collisions at low temperatures, predicting the formation of translationally and rotationally cold molecular ion MgK + in the ground state electronic potential by stimulated Raman type process. Our results are important in the perspective of upcoming experiments aiming at merging cold alkali atom and alkaline-earth ion in a hybrid trap for the creation of cold molecular ions by photoassociation.
Alkaline-earth dimers are now been used, as new grounds for, testing fundamental physics laws, precision measurements and quantum computation. As a starting point for such experiments, one needs a very good knowledge of the electronic structure, energetics and long-range behavior of these molecular ions. We perform accurate ab initio calculations for the ground and low-lying excited states of Be2+, Mg2+, Ca2+ and Sr2+ molecular ions. We have also calculated the spectroscopic constants, electronic transition dipole moments, polarizabilities and long-range dispersion coefficients for the various alkaline-earth ionic dimers. We have extended our calculations to study heteronuclear species of alkaline-earth molecular ions, like BeCa+, and also mixed alkali alkaline-earth species like NaCa+. We calculated photoassociation (PA) pathways for formation of cold molecular ions and also studied corrections to the Born-Oppenheimer Hamiltonian: non-adiabatic couplings and hyperfine structure due to nuclear spins and electric quadrupoles. We believe, this work would lay foundation, not only for new experiments in ultracold physics and chemistry, but would also provide valuable starting point for theoretical calculations involving low temperature scattering and resonant charge transfer.